Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates

Walker, Theodore W.; Chew, Alex K.; Li, Huixiang; Demir, Benginur; Zhang, Z. Conrad; Huber, George W.; Lehn, Reid C. Van; Dumesic, James A.

doi:10.1039/c7ee03432f

Cited by 140 publications

(153 citation statements)

References 75 publications

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“…[22][23][24] GVL has thus been considered as one of the most important platform chemicals available in future lignocellulosic biorefineries. GVL possesses excellent solvent properties (e.g., solvation) for homogeneous and heterogeneous catalysis, [25][26][27][28][29][30][31][32][33][34][35] but it may also serve as stable and non-toxic platform chemical to be converted to a wide range of other useful chemicals.…”

Section: Introductionmentioning

confidence: 99%

Pentanoic acid from γ-valerolactone and formic acid using bifunctional catalysis

et al. 2020

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Section: Introductionmentioning

confidence: 99%

Pentanoic acid from γ-valerolactone and formic acid using bifunctional catalysis

et al. 2020

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“…More recent work of BAS catalyzed dehydration and hydrolysis reactions studied how the energetics of proton transfer to reactants with varying hydroxyl groups densities (hydrophilicity) is affected by the composition of organic solvents mixed with water. Organic co-solvents caused water-enriched domains to form in the vicinity of reactant hydroxyl groups, increasing hydroxyl group hydrogen-bonding strength with neighboring water molecules, and leading to stabilized proton transfer and protonated transition states compared to pure water 41 . An exhaustive study of mixtures of water with either DMSO, dioxane, THF, GVL, or acetonitrile demonstrated that molecular-scale interactions form multicomponent solvent clusters with highly varying proton affinities compared to either pure component.…”

Section: Resultsmentioning

confidence: 99%

Understanding solvent effects on adsorption and protonation in porous catalysts

Gould

Cho

et al. 2020

Nat Commun

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Solvent selection is a pressing challenge in developing efficient and selective liquid phase catalytic processes, as predictive understanding of the solvent effect remains lacking. In this work, an attenuated total reflection infrared spectroscopy technique is developed to quantitatively measure adsorption isotherms on porous materials in solvent and decouple the thermodynamic contributions of van der Waals interactions within zeolite pore walls from those of pore-phase proton transfer. While both the pore diameter and the solvent identity dramatically impact the confinement (adsorption) step, the solvent identity plays a dominant role in proton-transfer. Combined computational and experimental investigations show increasingly favorable pore-phase proton transfer to pyridine in the order: water < acetonitrile < 1,4dioxane. Equilibrium methods unaffected by mass transfer limitations are outlined for quantitatively estimating fundamental thermodynamic values using statistical thermodynamics.

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“…Based our findings and previous research, at entative mechanism is proposed for the dehydration of fructose to HMF catalyzed by PVP@[SO 3 H] 0.17 -SO 3 H( Figure S24). [16] To examine the stability as well as recyclability of the catalytic material, PVP@[SO 3 H] 0.17 -COF was used as ac atalyst up to five times.A sd epicted in Figure S25, HMF was obtained in 97.1 %yield even after five runs and no significant loss of activity was observed. Ah ot filtration test revealed that the obtained activity is not related to any leaching of the catalytically active acid sites (no remaining activity in the supernatant).…”

Section: Angewandte Chemiementioning

confidence: 99%

Reaction Environment Modification in Covalent Organic Frameworks for Catalytic Performance Enhancement

et al. 2019

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Herein, we show how the spatial environment in the functional pores of covalent organic frameworks (COFs) can be manipulated in order to exert control in catalysis. The underlying mechanism of this strategy relies on the placement of linear polymers in the pore channels that are anchored with catalytic species, analogous to outer‐sphere residue cooperativity within the active sites of enzymes. This approach benefits from the flexibility and enriched concentration of the functional moieties on the linear polymers, enabling the desired reaction environment in close proximity to the active sites, thereby impacting the reaction outcomes. Specifically, in the representative dehydration of fructose to produce 5‐hydroxymethylfurfural, dramatic activity and selectivity improvements have been achieved for the active center of sulfonic acid groups in COFs after encapsulation of polymeric solvent analogues 1‐methyl‐2‐pyrrolidinone and ionic liquid.

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Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates

Abstract: Experiments and molecular simulations are combined to understand organic solvent effects, enabling prediction of acid-catalyzed reaction rates for biomass conversion.

Cited by 140 publications

References 75 publications

Pentanoic acid from γ-valerolactone and formic acid using bifunctional catalysis

Pentanoic acid from γ-valerolactone and formic acid using bifunctional catalysis

Understanding solvent effects on adsorption and protonation in porous catalysts

Reaction Environment Modification in Covalent Organic Frameworks for Catalytic Performance Enhancement

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